This invention relates to terminating a gas-phase olefin polymerization reaction using a Ziegler-Natta catalyst system.
Olefin polymerizations using Ziegler-Natta catalyst systems are well known in the art. Recently, olefin polymerization in the gas phase has become commercially significant. In gas phase polymerization processes there is a need for a method to terminate the polymerization reaction rapidly and effectively in an emergency situation, while providing a method to restart polymerization without serious difficulty.
Polymerization of olefins, such as propylene or ethylene, in slurry or bulk phase processes can be terminated by addition of substances such as alcohols, ketones, ethers, aldehydes, carboxylic acids, phenols, water, oxygen, and carbon oxides. However, the effectiveness of such substances in gas-phase polymerizations is not predictable because the contact between a catalyst and a catalyst termination agent in a gas phase reactor generally is not as good as in a liquid phase reactor and especially the ability to restart a polymerization reaction after deactivation is uncertain.
It was found that isopropanol was successful in terminating a gas phase propylene polymerization, however it is difficult to mix uniformly a small volume of liquid isopropanol with a bed of polymer. Further, it was found that catalyst killed with isopropanol cannot be restored to a satisfactory fraction of original activity by any known method.
In a gas phase polymerization system, it is vital to terminate the reaction in an emergency shutdown condition with the ability to restart polymerization efficiently. If polymerization is terminated by a method such as use of isopropanol which permanently stops growth of polymer around a catalyst particle, the entire inventory of polymer in the reactor might need be replaced before restarting polymerization which would represent a time-consuming and costly operation.
We have discovered a method to terminate a gas phase olefin polymerization reaction while maintaining the ability to restart the reaction.